Certain water-soluble high molal oxyalkylated esters and method of making same



' Patented Nov. 21, 1944 2,363,047

UNITED STATES PATENT OFFICE.

CERTAIN WATER-SOLUBLE HIGH MOLAL OXYALKYLATED ESTERS AND NIETHOD OF MAKING SAME Melvin De Groote, University City, and Bernhard Keiser, Webster Groves, Mo., assignors to Petrolite Corporation, Ltd., Wilmington, Del., a corporation of Delaware tadecaethylene glycol.

' No Drawing.

Original application March 21,

1941, Serial No. 384,602. Divided and this'application June 26, 1942, Serial No..448,688

12 Qlaims. (01. 260-4045) This invention relates to a new chemical product 01'' compound. our present application being a division of our co-pending application Serial No. 334,602 filed March 21, 1941, which subsequently matured as U. S. Patent No. 2,295,170,

dated September 8, 1942.

One object of our present invention is to provide a new material, compound or. composition of matter, that is capable of use for various purposes, and particularly adapted for use as a demulsifier in the resolution of crude oil emulsions.

Another object of our invention is to provide 'a practicable method for manufacturing said 'new a polybasic carboxy acid, which, similarly, may

conveniently be indicated as being of the dibasic type, by the formula HOOC.D.CO0H, in which D is a dicarboxy acid residue, then the fractional ester obtained by reaction between equimolar quantities may be indicated by the following form a:

HOOC.D.COQ.T

The polyethylene glycol may be characterized by materials or the kind such as heptaethylene glycol, octaethylene glycol, nonaethylene glycol, decaethylene glycol, to and including hep- For convenience, these polyethylene glycols may be indicated by the following formula:

in which m varies from 7 through 17.

Instead of polyethylen glycols, one may use polypropylene glycols or poly-butylene glycols.

Thus, for convenience, in the broadest aspect,

the polyalkylene glycols employed may be indicatedby "he following formula:

, in which m has its previous significance and n acid itself.

inafter stated, by the neutral ester derived by esterification of one mole of a glycol of the kind above described, with two moles of a fractional ester of the kind previously described. The formation of the compound may be indicated by the following reaction, although obviously, it is immaterial what particular procedure is employed to :produce the particular chemical compound or product:

- As indicated previously, the polybasic acids employed are limited to the type having not more than six carbon atoms, for example, oxalic,

malonic, succinic, glutaric, and adipic. Similarly, one may employ acids such as fumaric, maleic, glutaconic, and various others, includ ing citric, malic, tartaric, and the like. The se lection of the particular tribasic or dibasic acid .employed is usually concerned largely with convenience of manufacture of the finished ester, and also of the price of the reactants. Generally speaking, the higher the temperature employed, the easier it is to obtain large yields of.

the esteriiied product Although oxalic acid is comparatively cheap, it decomposes somewhat readily at slightly above the boiling Point of water. For this reason, it is more desirable to use an acid which is more resistant to pyrolysis. Similarly, when a polybasic acid is available in the form of an anhydride, such anhydride is apt to produce the ester with greater case than the For this reason, maleic anhydride is particularly adaptable; and also, everything else considered, the cost is comparatively low on a per molar basis, even though somewhat higher on a per pound basis.- Succinic acid or the anhydride has many of the attractive qualities of maleic anhydride; and this is also true of adipic acid. For purposes of brevity, the bulk of the 'compounds'hereinafter illustrated will refer to the use of maleic anhydride, although it is understood that any other suitable polybasic acid may be employed. Furthermore, for purposes of convenience, reference is made to the use of polyethylene glycols. As has been previously indicated, such glycols can be replaced by suitable polypropylene or polybutylene compounds.

As far as the range of oxyalkylated compounds employed as reactants is concerned, it is our preference to employ those having approximately 8-12 oxyalkylene groups, particularly 8-12 oxyethylene groups. The preference to use then ethylated compounds is due largely to the fact that they are commercially available, and particularly so "in two desirable forms, The most desirable form is the so-called nonaethylene glycol, which, although consisting largely of nonaethylene glycol, may contain-small amounts of heptaethylene and octaethylene glycols, and possibly minor percentages of the higher homologs. Such .glycols represent the upper range of distillable glycols; and they may be conveniently referred to as upper distillable ethylene glycols. There is-no particularly good procedure for making a sharper separation on a commercial scale;

are available in the form of a. waxy water-sol-- uble material, and the general range may vary somewhat from decato tetradecaethylene glycol. As is well understood, the method of producing such glycols would cause some higher "homologs to be formed; and thus, evenin this instance there may be present some oxyethylene glycols'within the higher range above indicated. One need not point out that these particular 'compounds consist of mixtures, and that in some instances, particularly desirable esters are ob-' tained by making mixtures of the liquid nonaethylene glycol with the soft, waxy, lower nondistillable polyethylene glycols. For the sake of convenience, reference in the examples will be to nonaethylene glycol; and calculations will be based on a theoretical molecular weight of 414. Actually, in manufacture, the molecular weight of the glycol" employed, whether a'higher .distillable polyethylene glycol, or a lower n0ndis tillable polyethylene glycol, or a mixture of the same, should be determined and reaction conducted on the basis of such determination, particularly in conjunction with the hydroxyl or acetyl value.

It has been previously pointed out that it is immaterial how the compounds herein contemplated are manufactured, although we have found it most desirable to react the selected gly- I col or mixtures of glycols with maleic anhydride in a ratio oftwo moles of the anhydride for one mole of the glycol. Under such circumstances, we have found little tendency to form longer chain polymers; and in fact, the product of reaction, if conducted at reasonably low temperatures, appears to be largelymonomeric. For convenience, such intermediate product may then be considered as a d ibasic or polybasic acid. 'On'e mole-of the intermediate so obtained is then reacted with' two moles of the alcoholic material of the kind subsequently described.

It is to be noted, however, that if one prepares, a fractional acidic ester, ,then if two moles of thefractional acidic ester are reacted with one mole of the polyethylene glycol, thereis no postypes of condi-- I 70 unsaturated acids are most readily obtained by sibility for the formation of polymeric esteriflcation products under ordinar tions.

The alcoholic compounds employed as reactants in the manufacture of the new compounds or reagents herein'described, are materials conveniently referred to as'theamides of high molar -alcohol acids or high molar hydroxy acids.

20 from the hydroxylated compounds.

ated acids are produced by other procedures. such'as chlorination, either by addition or sub- Such amides are derived from the high molar hydroxy acids. Like the high molar hydroxy acids they are invariably water-insoluble. Since the amides are derivatives of the high molar hydroxy acids, it is most convenient to indicate the variety of high molar hydroxy acids which may be converted into amides or-substituted amides. The commonest example of a high molal hydroxy acid is ricinoleic acid. Other hy- 10 droxy fatty acids include hydroxystearic acid,

dihydroxystearic acid, diricinoleic acid, aleuritic acid, and the like. Similar acids are obtained in the oxidation of paraffin, petroleum hydrocarbons, or wax, and are commonly referred to as hydroxylated wax acids. Hydroxylated wax acids occur as by-products in the oxidation of waxes or similar materials, and are usually separated so that the commonest commercial form of oxidized wax acids represent mixtures comparatively free Hydroxylstitution, as, for example, chlorination of oleic acid or stearic acid. Subsequent reactions in- I volve the removal of. the chlorine with the introduction of a hydroxyl radical. Undecylenic acid, derived from castor oil, has been converted into a hydroxy undecenoic acid. Unsaturated hydroxy acids, such as ricinoleic acid, may be treated in various manners, so as to produce derivatives, for example, chlorinated or brominated ricinoleic acid. Such materials are entirely satisfactory for use as reactants in the preparation of materials of the kind herein contemplated.

Naturally-occurring naphthenic acids can also be converted into hydroxylated products by follow- I ing similar procedure. An unsaturated hydroxy acid, such as ricinoleic acid, can be converted into a hydroxylated aryl-stearic acid. Such procedure contemplates reactions such as those involving ricinoleic acid, benzene, and aluminum chloride in large excess, or involves the desulfonation' of a sulfo-aromatic fatty acid. In any event, by employing derivatives of undecylenic acid, or

one or more of the various wax acids, naturallyoccurring naphthenic acid, ricinoleic acid, diricinoleic acid, or derivativesthereof, as previously explained, one can obtain a variety of hydroxylated monocarboxy acids, having at least 59 11 carbon atoms andmotin excess of 36 carbon atoms. Such compounds are the kind herein contemplated as reactants to furnish the alcoholiform hydroxyl.

Hydroxyaclds or the kind herein contemplated as reactants for the formation .of amides, may.

also be prepared by the hydrolysis of alphahalogen acids. For instance, alpha-bromocaproic acid, alpha-bromocaprylic acid, alphabromocapric acid, alpha-bromolauric acid, alpha- 60 bromomyristlc acid, alPha-bromopalmitic acid,

and the like,can be hydrolyzed togive the correspondingalpha-hydroxy; acid. Indeed, a re active alpha-halogen acid may serve 'as a functional equivalent of analpha-hydroxy acid by liberation of hydrochloric acid, instead of water.

Such type o freaction, however, involves numerous difiiculties; and thus, it is better to employ a hydroiw acid.

In some instances derivatives of hydroxylated 'rivative in which anaryl group is introduced.

Such derivatives can then be saponifled or hydrolyzed so as to regenerate the hydroxyl radical. The manufacture of amides from acids is, of

course, comparatively simple. One may employ dimaleate. The reaction may be shown more simply as if involving the acid instead of the anhydride, thus:

vriooccllaucoo:igiiiijcrmcmooinpcrsififfif i ooc.o,u..coo11 the acid or a suitable derivative, such as the acyl halide, or preferably, the ester. In many in stances it is easier to obtain the amide from an ester derived from a monohydric or polyhydric alcohol than it is from the acid itself.

As to the manufacture of various esters from acids of the kind above described, attention is directed to the following United States patents, to wit: Patents Nos. 1,160,595, dated Nov. 16,1915, to Gruter et al.; 2,221,674, Nov. 12, 1940, Ellis;

and 2,177,407, Oct. 24, 1939, Hansley. See also Organic Syntheses, volume X, page 88.

In any event, the acid or suitable derivative,

particularly the ester, is treated with ammonia to aniline, cyclohexylamine, 'or the like, are substituted for ammonia, one obtains a substituted amide which can be employed satisfactorily in the present. process, provided, of course, that the final product is water-soluble. In fact, secondary amines, such as dibutylamine and diamylamine, can be used. Since such materials are generally more expensive than ammonia, and since the hydrocarbon groups present tend to decrease water solubility, there is no added advantage in using such materials, except for some special purposes, such as the resolution of oil field emulsions. If such materials are used, it is preferable that they be derivatives of primary amines, i'. e., that the substituted amide contain only one hydrocarbon group, and in any event, that such hydrocarbon group contain not more than 7 carbon atoms, as, for example, derivatives of monoamylamine, yclohexylamine, aniline, and benzylamine. 1

In the hereto appended'claims reference to amides is intended 'to include substituted amides in which there is present not more than one hydrocarbon group containing not more than 7 carbon atoms, provided that such materials serve as obvious functional equivalents, i. e., yield water-soluble products. The hereto appended,

claims are not intendedto include substituted amides derived from amines containing hydroxy hydrocarbon radicals, as, for example, monoethanolamine, monopropanolamine, tris(hydroxymethyl) aminomethane, monoglycery'lamine, etc; 1

' INTERME IATE PRoDuc Example 1 One pound mole of nonaethylene glycol is reacted with two pound moles of maleic anhydride INTERMEDIATE PRoDue Example 2 A mixture of lower non-distillable polyethylene glycols, representing approximately vdecato tetradecaethylene glycol, is substituted for nonaethylene glycol in'the preceding example.

INTERMEDIATE PRODUCT Example 3 A -50 mixture of nonaethylene glycol and lower non-'distillable polyethylene glycols of the kind described in the previous example is substituted for nonaethylene glycol in Example 1.

I INTERMEDIATE PRODUCT.

' Example 4 Adipic acid is substituted for maleic anhydride in Examples 1-3, preceding.

I INTERMEDIAT PRODUCT Example 5 Oxalic acid is substituted for maleic anhydride in Examples 1-3, preceding.

INTERMEDIATE PRoDucT Example .6

Citric acid is substituted for maleic anhydride in Examples 1-3, preceding.

INTERMEDIATE Paonuc'r Example 7 Y Succinic anhydride is substituted for maleic anhydride in Examples 1-3, preceding.

- COMPOSITION or MATTER Example 1 One pound mole of the intermediate product of thekind described in Intermediate product, Examples 1, 2 and 3, above, is reacted with two pound moles 'of ricinoleoamide, untilsubstantially all dibasic carboxyl acidity has disappeared. Time of reaction may vary from a few hours to as much as 20 hours. The reaction may b indi-.

cated in the followingmanner: I

i E H" v H i l.

:HiORCON\ Nocnogg H 11 (In the above I-IORCO is the ricinoleyl radical.)

COMPOSITION or MATTER Example 2 The amide of hydroxystearic acid is substituted for ricinoleoamide in the preceding example.

COMPOSITION or .MA'ITER Example 3 The amide of dihydroxystearic acid is substituted for ricinoleoamide in Composition of matter, Example 1.

so as to form nonaethylene glycol dihydrogen substituted for ricinoleoamide in Composition of matter, Example 1. J

COMPOSITION or MATTER Example 6 A mixture of hydroxylated oxidized wax acids having an average molecular weight of approximately 250-275, is converted into the correspond- "ing mixture of amides and substituted for ricin- Oleoamide in Composition of matter, Example 1.

COMPOSITION OF- MATTER Example 7 A mixture of hydroxylated'oxidized wax acids having an average molecular weight of approximately 275-300, is converted into the corresponding mixture of amides and substituted for ricinoleoamide in Composition of matter, Example 1. K

COMPOSITION OF MATTER V Example 8 I A mixture of hydroxylated, oxidized wax acids I having an average molecular weight of approximately 300-325, converted into the corresponding mixture of amides and substituted for ricinoleoamide in Composition of matter, Example 1.

COMPOS TION OF MATTER Example 9 '6, is substituted for that in Intermediate pro'd- In Composition of matter, Examples 1-8, pre- I ceding, any residual acidity present is removed by cautiously adding a dilute solution ammonium hydroxide until the resultant product gives a clear, limpid solution inwater, particularly in dilute form.

COMPOSITION or MATTER I Example 10 In Composition of matter, Examples 1-8, preceding, any residual acidity present is removed by cautiously adding a dilute solution of triethanolamine until the resultant product gives a clear, limpid solution in dilute form.

COMROsITIoN OF MATTER Example 11 In Composition of matter, 'Examples 1-8, preceding, any residual acidity present is removed by cautiously adding a dilute solution of tris- (hydroxymethyl)aminomethane until the, Tesultant product gives a clear, limpid solution in water, particularly in dilute form.

COMPOSITION or MATTER Example 12 Thesame procedure is followed as in Composition of matter, Examples 1-11, inclusive, except that an intermediate product of the kind exemplified by Intermediate product, Example 4, is substituted for that in Intermediate product, Examples 1, 2 and 3.

Water, particularly in COiuPOsITIoN OElVLATTER Example 13 I The same procedure is followed as in Composition of matter, Examples'l-ll, inclusive, ex-

cept that an intermediate product of the kind exemplified by Intermediate product, Example 5, is substituted for that in Intermediate product,

Examples 1,2 and ,3.

ComrosrTIoN or MATTER Eaiample 14 The same procedure is followed as in Com position'oi matter, Examples '1-11, inclusive, ex cept that an intermediate product of the kind exemplified by Intermediate product, Example uct, Examples =1, 2 and 3.

COMlOSITION OF MATTE Example 15 The same procedure is followed as in Composition of matter, Examples 1-11, inclusive, except that an intermediate product of the kind exemplified by Intermediate product, Example.

product,

'7, is substituted for that in Intermediate Examples 1, 2 and 3.

It is to be noted that this second step is an esterification reaction, and the same procedure is employed as suggested above in the preparationv of the intermediate product, Needless to say, any particular method may be used to produce the desired compounds of the kind indlcated. In some instances it may be desirable to conduct the esterification reaction in the presence of a non-volatile-inert solvent, which simply actsas a diluent or viscosity reducer.

In the preceding examples, attention hasbeen directed primarily to the momomeric form, or at least, to the form in which the bifunctional alcohol, i. e., a glycol, and the poly-functional acid, usually a bifunctional compound, react to give a chain type compound in which the adjacent acid and glycol nucleus occur as a structural unit.

For instance, in the monomeric form this may be indicated in the following manner:

acid glycol acid If, however, one prepared an intermediate product employing the ratio of three moles o1 maleic anhydride and twoinoles of nonaethylene glycol, the tendency would be to produce a prodnot which might be indicated in the following manner: 6

acid glycol acid. glycol acid Similarly, threemoles of the glycol and four moles of the acid might tend to give a combination which may be indicated thus:

acid glycol acid glycol acid glycol acid AnOtherWay of stating the matter is that the composition may be indicated in the following manner:

in which the, characters have their previous sig nificance and a: is a relatively small whole number less than 10 and probably less than 5; and in the monomeric form-0:, of course, is 1. The

limitations on'the size of a: are probably influenced largely by the fact that reaction leading to ifzurther growth is dependent upon random conact.

Some of the products. are self-emulsifiable oils or self-emulsifiable compounds; whereas, others able type is characterized by giving a clear solution in water, and usually in the presence of soluble calcium or magnesium salts, and frequently in the presence of significant amounts of either acids or alkalies,

Water solubility can be enhanced in a number of ways which have beensuggested by previous manufacturing directions, for instance: 7

l (a) By using a more highly polymerized ethylene glycol; v

' (b) By using a polymeric form instead of a monomericform in' regard to the unit which forms the chain between the two alcoholic nuclei;

(o) By using a polybasic carboxy acid of lower molecular weight, for instance, maleic acid'instead of adipic acid;

(11) By using an alcoholic material of lower molecular weight, for instance, ricinoleoamide, instead of the amide of a hydroxylated wax acid of a higher molecular acid, or instead of a substituted amide, such as amyl ricinoleoamide.

In any event, it' is to be noted that the compounds of the type herein contemplated are limited to the water-soluble type, i. e., those which I by any suitable base, for instance, ammonia, triethanolamine, or the like, especially in dilute solution. Naturally, precaution should be taken so that neutralization takes place without saponification or decomposition of the ester. In some cases there is no ,objection to the presence of the acidic group. Indeed, if a tribasic acid be employed in such a manner as to leave one free carboxyl group, then it is usually desirable to neutralize such group by means of a' suitable. basic material.

In the hereto appended claims, reference to a neutral product refers to one in which free carboxylic radicals are absent.

Materials of the kind herein contemplated may find uses as wetting, detergent, and leveling agents in the laundry, textile, and dyeing industry; as wetting agents and detergents in the acid washing of fruit, in the acid washing of building stone and brick; as a wetting agent and spreader in the application of asphalt in road building and the like, as a constituent of soldering flux preparations; as a flotation reagent in the flotation separation of various minerals; for flocculation and coagulation of various aqueous suspensions containing negatively charged particles such as sewage, coal washing waste water, and various trade wastes and the like; as germicid'es,

insecticides, emulsifiers for cosmetics, spray oils,

water-repellent textile finish, etc. These uses are by no mea exhaustive. a

' However, the ost important phase of the present invention, as'far as industrial application goes, is concerned with the use of the materials previously described as demulsifiersfor water in-oilemulsions, and more specifically, emulsions of water or brine in crude petroleum.

,We have found that the particular chemical compounds or reagents herein described and desirable for use as demulsiflers, may also be used for other purposes, for instance, as a breakinducer in doctor treatment of the kind intended to sweeten gasoline. See U. S. Patent No. 2,157,223, dated May 9, 1939, to Sutton. 7

Chemical compounds of thekind herein described are also of value as surface tension depressants in the acidization of calcareous oilbearing strata by means of strong mineral acid,

' such as hydrochloric acid. Similarly, some memand Keiser. As to using compounds of the kind herein described as demulsifiers, or in particular as surface tension depressants in combination with mineral acid or acidization of oil-bearing strata, reference is made to U. S. Patent No. 2,233,383, dated February 25, 1941, to- De Groote and Keiser. i

It will be apparent to those skilled in the art that residual carboxylacidity can be eliminated by esterificationwith a low molal alcohol, for innesium' salts, for such property is of particular:

value. Usually, however, neutralization with a dilute solution of ammonia or the like is just as practicable and less expensive. What has been said previously canbe recapitulated and presented in more formal agreement with customary nomenclature in the following manner: As stated previously, in the broadest aspect, the polyalkylene glycols employed may be indicated by the following formula:

OH(cnH2nO)mH in which an has its previous significance, and n represents a numeral varying'from' 2 to 4. In

similar form this structure can be indicated in the following manner:

in which the divalent radical '-Rois the divalent radical---(CnHanO)m-as previously defined. L

The dibasic acid previously referred to, in its sim lest form as HOOC.D.COOH, is more completely portrayed by the following formula:

00011 Rr-dOOH (ooonw in which R1 is the polybasic carboxy acid residue,

except inthe unique case of oxalic acid, and n is the numeral 0 or '1, depending on whether or A not the polybasic acid is dibasieor tribasic.

If the polybasic acid just described is indicated by R', and if the glycol just described is indicated in which p and 11' represent numerals varying from 1 to 10, and 1)" represents a numeral varying from 1 to 20, and R and B" have their prior significance, and the ratio of p to p varies from 2:1 to p+1:p', with the obvious proviso that such acidic ester must contain at least two free carboxyl radicals.

Similarly, the high molal hydroxy amide may be indicated'by the following formula:

carbon atoms, and n has its prior significance,

i. e., being the numeral or 1, depending on whether the acid is monohydroxylated or dihydroxylated, and R: and R4 are selected from the class of hydrogen atoms, and hydrocarbon radicals having not over '7 carbon atoms, and may be the same or difierent.

, The new composition of matter herein contemplated is best represented as an ester obtained by the esterific'ation reaction involving the acidic fractional ester above described and the hydroxylated amide previously mentioned. The final composition may be obtained in any suitable manner and would properly represent the final product, regardless of the succession of, the intermediate steps. So portrayed, the structural I formula is as follows:

[egege I in which all of the characters have their prior significance, and n" represents a numeral varying from 1 to 3, and n' represents a numeral varying from 1 to 4,.

It has been previously pointed out in the specification that any residual carboxylic radicals, and especially one obtained from tribasic acids, could be neutralized with a variety of suitable basic materials. In other words, a residual carboxylic atom may be replaced by a metallic atom, an ammonium radical, or substituted ammonium radicals, as previously indicated. Under such circumstances, any residual carboxylic radical, instead of appear thus: COOH, may, in essence,

' be the radical COOR5 in which R5 represents a cation including the acidic hydrogen atom.

This can be best disposed of by rewriting the formula for the polybasic carboxy acid, thus:

COOH

R1-C0OH in which all of the characters have their prior significance.

Having thus described our invention, what we claim as new and desire to secure by Letters Patent is:

1. A water-soluble ester of the formula:

; M- a] l which radical, in turn, represents a numeral varying from 2 to 4, and m represents a numeralvarying from 7 to 17 R" is the polycarboxy acid coon Rr-COOH in which R1 is the polycarboxy acid residue, and

.1% is a cation, and as previously, 11. is the numeral 0 or 1;

HO R: I

' moon no ai is an amide in which is the acyl radical of a high molal hydroxy acid having at least 11 and not more than 36 carbon atoms, and n is the numeral 0 or 1, and Raand R4 are selectedfrom the class of hydrogen atoms bon atoms.

2. A water-soluble ester, as defined in claim 1, wherein all occurrences of n are 0.

5 3. A water-soluble ester, as defined in claim 1,

wherein, all occurrences oin' are 0, and n represents the numeral 2.

4. A water-soluble ester, as definedin claim 1, wherein all occurrences of n are 0, n represents the numeral 2, and m represents a numeral varying from 7 to 11.

5. A water-soluble ester, as defined in claim 1, wherein all, occurrences of n are 0, n represents the numeral 2, m represents a numeral varying from 7 to 11, and R200 is an 18 carbon atom fatty acid residue.

6. A water-soluble ester, as defined in claim 1, wherein all occurrences of n are 0, n represents the numeral 2, m represents a numeral varying from 7 to 11, RaCO isan 18 carbon atom fatty acid residue, and the ratio of p to p is 2 to 1.

7, A water-soluble ester, as defined in claim 1,

wherein all occurrences of'n' are 0, n represents the numeral 2, m represents a numeral varying from 7 to 11, RzCO is an 18 carbon atom fatty acid residue, the ratio of p to p is 2 to 1, and with added neutralization of all residual acidity".

8. A water-soluble ester, as defined in claim 1, wherein all occurrences of n are 0, n represents the numeral -2, m represents a numeral varying and hydrocarbon radicals having not over 7 car;-

2,353,047 flrrqmv tolLRacflisaricinoleic acldresldue,

the ratio of p to p is 2 to 1, and with added neutralizatlon of all residual acidity.

9. A water-soluble ester, as definedin claim 1,

7 wherein all occurrences of n arel), nrepresents the numeral 2, m represents a numeral varying from 7 to 11, RzCO is a ricinoleic acid residue, the ratio of p to p is 2 to 1, with added neutralization of all residual acidity, and R1 is an adipic acid residue.

10. A water-soluble ater, as defined in claim 1, wherein all occurrences of n are 0, n represents the numeral 2, m represents a. numeral varying from I to 11, Rico is a ricinoleic acid residue,

ization of all residual acidity; and Rris a succinic acid residue.

11. A water-soluble ester, as defined in claim 1, wherein all occurrences of 1; are 0, n represents the numeral 2, m represents a numeral varying Irom'lto 11,1hCOisaricmoleicacidresidue, the ratio ofptop' is2to Lwithaddedneutralization atoms, with .a polybasic carboxy acid having not more than 6 carbon atoms, in a predetermined ratio of more than one and not over 2 moles or the polybasic acid for each mole of the glycol, to produce a water-soluble product; and (13) reacting one mole of the aforementioned polybasic compoimd produced by esterification, with two moles of the amide of a high molar hydroxy acid having'at least 11 carbon atoms and not more than 36 carbon atoms, and containing at least one hydroxyl radical as part of the acyl group, an soas to produce a water-soluble product.

MELVIN DE GROOTE.

BEZNHARD 

